JPS59169928A - Recovery of gallium - Google Patents

Abstract

PURPOSE:To achieve the effective adsorption of Ga and to lower the equilibrium concentration of Ga, by contacting a solution containing Ga with a chelate resin having a specific structure in the molecule. CONSTITUTION:A chelate resin having the structure of formula (Ar1 and Ar2 are same or different cyclic group; M1 and M2 are thiol group, hydroxyl group, dithiocarbamic acid group or aminoalkylenephosphoric acid group; X is a molecular chain containing atom of Lewis base) is synthesized, and is made to contact with a solution containing Ga. Ga can be efficiently adsorbed and the equilibrium concentration of Ga can be lowered by this process.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering gallium from solutions containing potassium.

More specifically, it relates to a method of adsorbing and recovering gallium in a solution using a special chelate resin.

Commercial production of potassium is carried out from alumina production Bayer liquid, waste cocoon waste, aqueous sodium aluminate solution, and aqueous zinc ore acid leaching solution. Conventionally, there are two methods for recovering gallium from an aqueous solution of sodium aluminate: 1. Electrolyzing with mercury as a cathode, converting potassium in the solution into amarcum, and hydrolyzing the amarcum with caustic alkali to collect the resulting gallium. A method of electrolyzing and recovering an acid-alkali aqueous solution, and a solution in which the alumina content in the sodium aluminate aqueous solution (K) is mainly precipitated by blowing carbonate scum into the sodium aluminate aqueous solution, and a solution with an increased ratio of alumina content and gallium content. A method is employed in which carbon dioxide gas is blown into the solution to co-precipitate the alumina and potassium components, the coprecipitate is dissolved in caustic alkali, and the resulting aqueous alkali carminate solution is then electrolyzed and recovered. In addition, the method for recovering potassium from zinc ore acid leaching aqueous solution is to calcinate the zinc concentrate, then extract the zinc leaching residue from which most of the zinc is extracted, and then leaching with sulfuric acid and decoppering, followed by multiple extractions. A method has been adopted in which the gallium cake obtained through the process is dissolved in an alkali, and the resulting aqueous carminic acid aqueous solution is electrolyzed and recovered.

However, the former method of recovering potassium from a sodium aluminate aqueous solution has the disadvantage that a large amount of mercury is dissolved and lost in the aluminate aqueous solution during amalgamation, and the latter method □ has the disadvantage that the caustic alkali content in the sodium aluminate aqueous solution is carbonated and lost due to the use of carbon dioxide gas. In addition, when using zinc ore acid leachate, there is a disadvantage that it requires a complicated extraction process because it contains various impurity elements.

ft, as a method for recovering potassium in Bayer's solution, gallium is recovered from an aqueous sodium aluminate solution by liquid-liquid extraction using an extractant consisting essentially of water-insoluble substituted hydroxyquinolines and an extraction solvent consisting of an organic solvent. Methods have been proposed (Japanese Patent Application Laid-open No. 51-82411, Japanese Patent Application Laid-open No. 58-52289, Japanese Patent Application Laid-Open No. 64-9972).
However, in this method, the reagent used has poor alkali resistance, the substituents decompose during long-term use, the water solubility increases, and the recovery rate of the reagent and potassium decreases. Since the potassium recovery reagent is a liquid, a considerable amount of the recovery reagent is lost as it is dispersed and dissolved in the sodium aluminate (rum aqueous solution), and furthermore, the quality of the aluminum hydroxide is adversely affected due to the extraction agent being mixed in during the transportation process. There is a drawback that there is a risk of -4 when the speed is extended, and it has not yet been industrially satisfied.

・In view of these circumstances, the present inventors conducted extensive research to find a method for recovering gallium that overcomes the above-mentioned disadvantages, and as a result, they found that Kir-1 resin, which has a specific functional group, selectively collects potassium. The present invention was completed based on the discovery that adsorption occurs.

That is, the present invention provides a force having the general formula % (where Ar1 and Arz are the same or different cyclic compounds, M
1 and M2 represent a naol group, a dithiocarbamate group, or an aminoalkylene v4f group, and X represents a molecular chain containing a Lewis base atom. The present invention provides a method for recovering gallium contained in a solution, which comprises bringing an oxyto resin having a functional group represented by the following formula into contact with a solution containing gallium.

The chelate resin used in the present invention is not particularly limited as long as it has a functional group represented by the above general formula in its molecule.

Arl and Ar2 in the above general formula represent the same or different cyclic compounds, such as tuunyl group, phenylene group, naphthyl group, naphthylene group, anthryl group, anthrylene group, thioanthrenyl group, furyl group, etc. phenyl group and phenyl group are particularly preferred. X represents a molecular chain containing a Lewis base atom, more specifically, RI R2+<,
R.

　　　　0 ]111 -N-C-Y-C-N-, -N-s-y-s-N-.

l II: l l 1111I
11<] 0 0 R2, RI OU -R2(R
, +, R2 is the same or different hydrogen atom or alkyl group, sword is an integer of 1 to 5, Y is an alkylene group and/or phenylene group having 1 to 10 carbon atoms, Z is an alkyl group having 2 to 10 carbon atoms (representing a lydene group) can be mentioned.

R, R2 (R1+R2+Z are the same as above) is preferred.

Such chelate resins include chloromethyl group, sulfonyl chloride group, carbonyl chloride group, incyanato group, epoxy group, aldehyde group, 2) IJ group, and styrene having amine-reactive groups such as halogen atoms such as chlorine and bromine. , phenol, ethylene, propylene, vinyl chloride, acrylonitrile, α-chlorotecrylonitrile, vinylidene cyanide, methacrylonitrile, and other monomers (hereinafter referred to as resins with amine-reactive groups). has 7 primary or secondary amine groups,
and an amino compound having a functional group represented by the general formula %), for example, 5
-diethylenetriamino-2,2'-dihydroxy-N
, ■-ethylene dianiline, 5-ethylene diamino-2
, 2'-dihydroxy-N N'-ethylenedianiline, 5-amino-2,2'-dihydroxy-N, N'-ethylenedianiline, 5-amino-2,2'-dimercapto-N, N'- Ethanediylidene dianiline, 5-aminomethyl-2,2'-dihydroxy-N, N'-ethylenedianiline, 5-diethylenetriamino-2,2
'-dimercapto-N,N'-succinyldianiline,
5-Aminemethyl-2,2'-bis(dithiocarboxyamino) N,N'(8-azapentamethylene)dianiline, 5-diethylenetriamino-2,2'-bis(phosphonomethylamino)-NN''- (8-Asapentamethylene) dianiline, 5-amino-2,2'-bis(
phosphonomethylamine)-N,N'-C8-azapentamethylene)dianiline, 5-amino-2,2'-dihydroxy-N,N'-(p-xylenylene)dianiline,
A polymer obtained by reacting an amine compound such as 4-diethylenetriamino-2,2'-(2,5-diazaadipoyl)diphenol; ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, 1 in the resin obtained by reacting amine compounds such as tetraethylene pentamine, pentaethylene hexamine, hexamethylene diamine, and quanicine.
An aminated resin having a primary or secondary amine group has a chloromethyl group, a sulfonyl chloride group, a carbonyl chloride group, an incyanato group, an epoxy group, an aldehyde group,
Compounds having an amine-reactive group such as a halogen atom such as chlorine, bromine, or iodine, and a functional group represented by the general formula %) and derivatives thereof, such as 5-bromo-2,'2'-dihydroxy-N
, N'-ethylenedianiline 5-bromo-? , 2'
-dimercapto N, N'-ethanediylidenecyaniline, 5-chloromethyl-2,2'-dihydroxy-
N,N'-ethylenedianiline, 5-chloromethyl-2
゜2'-dimercapto-N, N'-ethanediylidene dianiline, 5-bromo-2-hydroxy-21-mercapto-N, R-succinyl dianiline, 5-bromo-2,2'-bis(dithiocarboxy amino)-N, N
'-(3-azapentamethylene)dianiline, 5-bromo-2,2'-dihydroxy-N, N'-(p-xylenylene)dianiline, 4-chloromethyl-2,2'-(
2,5-diazaadipoyl)diphenol, 5-bromo-2,2'-dimercap)-N,N'-hexamethylene dianiline, etc., or inorganic salts and derivatives of these compounds such as hydrochloride and sulfate. Examples include boiled polymers.

Therefore, gallium can be adsorbed and removed from strongly basic aqueous solutions such as sodium aluminate aqueous solutions used in the Bayer method alumina production process, or acidic gallium-containing aqueous solutions such as zinc ore acid leachate using the chelate resin having a functional group of the present invention. This means that it is completely unexpected that the chelate resin of the present invention would be extremely effective in recovering gallium from strongly basic or acidic gallium-containing aqueous solutions, since it has not been proposed at all in the past. Ta.

In carrying out the method of the present invention, the gallium-containing solution to be brought into contact with the chelate resin is usually a strongly basic or pH-containing solution.
An acidic gallium-containing aqueous solution of 0.5 to 3 is applicable, but of course other gallium-containing solutions can also be applied.

In particular, the treatment liquid used in the method of the present invention is a gallium-containing sodium 7 luminate aqueous solution (composition: Ga: 0.01-0.5y//, Zh: 20
-80 f/l, pH 0.5-3) is suitable.

In carrying out the method of the present invention, the contact between the chelate resin and the gallium-containing solution may be carried out under appropriately selected conditions. The contact method is not particularly limited, and for example, a method of immersing a chelate resin in a solution containing gallium, a method of passing a gallium-containing solution through a column filled with a chelate resin, etc. are generally employed.

However, from the viewpoint of processing operations, a method of passing a solution containing gallium through a column filled with a chelate resin is preferably employed.

In carrying out the method of the present invention, the amount of chelate resin used is not particularly limited and varies depending on the gallium concentration in the gallium-containing solution to be treated, the type of chelate resin used, etc. It can be set by doing the following.

Generally, the amount of chelate resin to be used may be selected as appropriate.

The contact temperature between the chelate resin and the potassium-containing solution is not particularly limited, but it is usually carried out at a temperature of 10 to 100°C.

Further, the contact time is not particularly limited, and a contact time of several seconds or more is usually sufficient.

The chelate resin from which gallium has been adsorbed and collected by the method of the present invention is then eluted and recovered with hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium sulfide, iminodiacetic acid, ethylenediaminetetraacetic acid, etc., or separated by heating to separate the chelate resin and gallium. Separate.

The potassium separated and recovered as described above can then be recovered as potassium metal by a known method, for example, by converting it into sodium galmate and electrolyzing it.

According to the method of the present invention as described in detail above, the adsorption capacity for potassium is extremely large compared to known gallium chelating agents, and the gallium equilibrium ratio can be lowered. The resin has the effect of being significantly superior in selective adsorption to gallium compared to known chelating agents.

In addition, the chelate resin of the present invention has alkali resistance and acid resistance, so it has the advantage of being particularly suitable for recovering gallium from Bayer first-step liquid and zinc ore acid leachate.

The method of the present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples unless the gist thereof is exceeded.

Example 1 2.21-Dihydroxy-N,N/-ethanediylidene dianiline was brominated with bromine in the presence of anhydrous aluminum chloride in a chloroform solvent, and then in a toluene solvent.
In the presence of pyridine, the Ly of the acrylonitrile-divinylbenzene copolymer resin having an aminated group with diethylenetriamine (hereinafter this polymer is referred to as chelate resin A) was adjusted to Ga801+v/l, Zn2B, 100 Cape/
l Zinc ore leachate containing 5Qd of pH 2.6 plus 3
After shaking for a period of time, it was filtered and the p liquid was analyzed for Ga and Zn, and the results shown in Table 1 were obtained.

Table 1 Examples 2-12 Chelate resin B; 5-chloromethyl-2,2'-dimercapto-N,N'
- A resin having a CH-CH 2 group obtained by reacting ethanediylidene dianiline with a styrene-divinylbenzene copolymer in a nitrobenzene solvent in the presence of anhydrous aluminum.

KIRE-1・Resin C; A resin obtained by aminating a chloromethylated styrene-dihinylbenzene copolymer with ammonia and 5-bromo-2-hydroxy-2'-mercapto-N, NJ-succinyl dianilide in a toluene solvent. , a resin having 111 0 groups obtained by reaction in the presence of pyridine.

KIRE-1・Resin D; Chloromethyl-dihinylben, which is obtained by aminating 5-bromo-2,2'-his(dithiocarboxyamino)-N,N'-(8-azapentamethylene)dianiline with diethylenetriamine. A resin containing a group obtained by reacting a ↓n copolymer with a toluene solvent in the presence of pyridine.

Chelate resin E; 5-Amino-2,2'-dihydroxy-N.

A resin having a group obtained by reacting N'-(p-xylenylene) dianione with chlorsulfone in a toluene solvent in the presence of pyridine.

Chelate resin F; acrylonitrile-dihinylbenzene, which is 4-chloromethyl-2.2'-(2.5-diazaazibo,yl)diphenol aminated with diethylenetriamine ffi
A rosin containing 0 groups obtained by reacting the combination with F in a toluene solvent in the presence of pyridine.

Chelate (Opening 11G; 5-bromo-2,2'-mercabutoNN'-hexamethylene dianiline was reacted with styrene-divinylbenzene copolymer in nitrobenzene solvent in the presence of anhydrous aluminum chloride. Resin with the obtained groups.

Chelate resin H: A resin having a group obtained by reacting 2,4-dihydroxyisophthalaldehyde with ethylenecyamine in a methanol-water solvent.

Chelate resin l゛N,N'-(5-bromo-2,2'-dihydroxylashif, nylethanedisulfonamide is reacted with an acrylonitrile-divinylbenzene copolymer aminated with ethylenediamine in a toluene solvent in the presence of pyridine. A resin with a group obtained by n.

After chloromethylating 2,2'-dihydroxy-N,N'-ethanediylidene di-naphthylamine with chloromethyl methyl ether in the presence of anhydrous zinc chloride in a chloroporm solvent to the chelate resin, A resin made by aminating Nirhenzen copolymer with ammonia,
A resin having an N=CH-CH=N group obtained by reaction in a toluene solvent in the presence of pyridine.

To chelate resin; 2.2'-dihydroxy-N of Example 1.

2,2' instead of N'-ethanediylidene dianiline
-Dihydroxy-N,N'-ethanediylidene dianthracene was used, but the resin had a group obtained by the same reaction.

Chelate resin L; 5-bromo-2,2'-bis(phosphonomethylamino)
-N, N'-(8-Asabeshitamethylene) dianiline is reacted with a chloromethylated styrene-divinylbenzene copolymer aminated with diethylene triaminohydride in toluene mB with a group obtained by reacting with a pyridine molecule. resin.

Each of the above chelate resins 1y was brought into contact with the zinc ore leachate 5' (1+++1) in the same manner as in Example 1, and the Ga and Zn in the P solution were analyzed. The results are shown in Table 2. Obtained.

Table 2 Examples 13-24 Fat A) used in Examples 1 to 22.

B, 'C, I), E, F, G, H, I, J, K.

■, each 5y of G, 11228mt/l, A144.
In addition to 100 - of a sodium aluminate aqueous solution from the alumina production process by the Bayer method containing 790 -/l, 13
After shaking for a period of time, the mixture was filtered and analyzed for GaA/ in the furnace solution, and the results shown in Table 3 were obtained.

□ \1, ゝ＼ \ Table 3 Procedural amendment (formality) April 22, 1982 Commissioner of the Patent Office 1.Display of the incident 1981 Patent barrel No. 43696 2, title of invention How to collect Susumuum 3 Person making the amendment Relationship to the case Patent applicant 5-15 Kitahama, Higashi-ku, Osaka (209) Sumitomo Chemical Co., Ltd. Representative Takeshi Tsuchikata 4 agents 5-15 Kitahama, Higashi-ku, Osaka Showa year, month, day (voluntary) 6 Target of correction Full text for details 7. Contents of correction Engraving of the statement (no changes to the details)

Claims (1)

[Scope of Claims] (X) The general formula (wherein Ar+ and Ar2 are the same or different cyclic compounds, Ml and Ml are a thiol group, a hydroxyl group, a dithiocarbamate group, or an aminoalkylene phosphate group, indicates a molecular chain containing a Lewis base atom.) A method for recovering potassium contained in a solution, which comprises bringing a chelate a-fat having a structure represented by the following formula into contact with a solution containing gallium. (2) Ar+ and Arz in the general formula are benzene rings,
The method for recovering gallium according to claim 1, characterized in that a chelate resin having a naphthalene ring or an anthracene ring is used. (3) Ml and Ml in the general formula are thiol groups and/or
The method for recovering gallium according to claim 1 or 2, characterized in that a chelate resin having a hydroxyl group or a hydroxyl group is used. (4) In the general formula, X is -N -C-Y - C−N −1 l 11 1+ 1 R,OOR2 00 1 −N −5−Y−8−N −, 1:l II I R+ 0 0 R2′ −LN=Z=N −1 (in the formula, R1, R2 is the same or different hydrogen atom or alkyl group, l is an integer of 1+5, Y is an alkylene group and/or phenylene group having 1 to 10 carbon atoms, Z is a carbon number 2 to
l. 3. A method for recovering RI-T according to claim 1.2 or 3, characterized in that a chelate resin is used. (5) Claim 1, characterized in that the potassium-containing solution is a sodium aluminate aqueous solution or a zinc ore acid leachate in the Bayer method alumina manufacturing process.
．． 2.3 or the method for recovering potassium according to item 4.